Waste and Biomass Valorization

, Volume 9, Issue 10, pp 1945–1954 | Cite as

Preparation of Double Carboxylic Corn Stalk Gels and Their Adsorption Properties Towards Rare Earths (III)

  • Fuchun Wang
  • Junmei Zhao
  • Huizhou Liu
  • Yuan Luo
  • Wankun WangEmail author
Original Paper


A novel biosorbent, corn stalk gels with double carboxylic groups synthesized by two oxidation steps (the double carboxylic groups modified adsorbent is abbreviated as DCCS-2), was prepared, characterized, and applied for the recovery of rare earths (III) from the nitric media. For the whole lanthanides, it exhibits a distinct “tetrad effect” with the increase of atomic numbers. Taking Nd(III) as a representative element, the adsorption capacity, kinetics, selectivity and mechanism were investigated. Thermodynamics and kinetic fittings were found to abide by Langmuir and pseudo-second-order rate equations and the corresponding parameters were calculated. The maximum adsorption capacity was calculated to be 2.44 mol/kg at 298 K for DCCS-2. Results showed that the double carboxylic groups played an important role for improving the adsorption capacity, e.g. the adsorption capacity of Nd(III) by DCCS-2 increased to 53.5 times compared to the raw corn stalk. Furthermore, DCCS-2 also shows a good selectivity between Nd(III) and many non-rare earth metal ions. The cation exchange is proposed to be the possible adsorption mechanism.


Adsorption Rare earths Waste biomass NaIO4 NaClO 



The raw corn stalk powder without chemical treatment


The activated corn stalk treated by NaOH solution


The modified corn stalk gels treated by NaOH and then by H2O2 solution


The modified corn stalk gels treated by NaOH and then by NaClO solution


The modified corn stalk gels treated by NaOH and then by NaIO4 solution


The modified corn stalk gels treated by NaOH, then by NaIO4 and then by H2O2 solution


The modified corn stalk gels treated by NaOH, then by NaIO4 and then by NaClO solution



This work was supported by the National Natural Science Foundation of China (Grant Nos. 51504073 and 51404081), the Joint Research Program of the Science and Technology Department of Guizhou Province [Grant Nos. QianKeHe LH (2014) 7373 and QianKeHe LH (2014) 7372], the Research Program of the Education Department of Guizhou Province [Grant No. QianJiaoKeHe KY (2015) 433], the Research Program of Talented Scholars of Guizhou Institute of Technology (Grant No. XJG20141104).

Supplementary material

12649_2017_9954_MOESM1_ESM.doc (482 kb)
Supplementary material 1 (DOC 482 KB)


  1. 1.
    Eliseeva, S.V., Bunzli, J.-C.G.: Rare earths: jewels for functional materials of the future. New J. Chem. 35, 1165–1176 (2011).CrossRefGoogle Scholar
  2. 2.
    Binnemans, K., Jones, P.T., Blanpain, B., Van Gerven, T., Yang, Y., Walton, A., Buchert, M.: Recycling of rare earths: a critical review. J. Cleaner Prod. 51, 1–22 (2013)CrossRefGoogle Scholar
  3. 3.
    Li, X.Z., Sun, Y.P.: Progress in solid–liquid extraction resin for separation of rare earth elements. J. Rare Earths. 23, 581–592 (2005)Google Scholar
  4. 4.
    Das, N., Das, D.: Recovery of rare earth metals through biosorption: an overview. J. Rare Earths 31, 933–943 (2013)CrossRefGoogle Scholar
  5. 5.
    Roosen, J., Binnemans, K.: Adsorption and chromatographic separation of rare earths with EDTA- and DTPA-functionalized chitosan biopolymers. J. Mater. Chem. A 2, 1530–1540 (2014)CrossRefGoogle Scholar
  6. 6.
    Vijayaraghavan, K., Sathishkumar, M., Balasubramanian, R.: Biosorption of lanthanum, cerium, europium, and ytterbium by a brown marine alga, Turbinaria conoides. Ind. Eng. Chem. Res. 49, 4405–4411 (2010)CrossRefGoogle Scholar
  7. 7.
    Das, N.: Recovery of precious metals through biosorption: a review. Hydrometallurgy 103, 180–189 (2010)CrossRefGoogle Scholar
  8. 8.
    Yakkala, K., Yu, M.-R., Roh, H., Yang, J.-K., Chang, Y.-Y.: Buffalo weed (Ambrosia trifida L. Var. Trifida) biochar for cadmium(II) and lead(II) adsorption in single and mixed system. Desalination Water Treat. 51, 7732–7745 (2013)CrossRefGoogle Scholar
  9. 9.
    Koduru, J.R., Chang, Y.-Y., Yang, J.-K., Kim, I.-S.: Iron oxide impregnated Morus alba L. fruit peel for biosorption of Co(II): biosorption properties and mechanism. Sci. World J. 2013, 14 (2013)CrossRefGoogle Scholar
  10. 10.
    Omidvar Borna, M., Pirsaheb, M., Vosoughi Niri, M., Khosravi Mashizie, R., Kakavandi, B., Zare, M.R., Asadi, A.: Batch and column studies for the adsorption of chromium(VI) on low-cost Hibiscus cannabinus Kenaf, a green adsorbent. J. Taiwan Inst. Chem. Eng. 68, 80–89 (2016)CrossRefGoogle Scholar
  11. 11.
    Lingamdinne, L.P., Koduru, J.R., Jyothi, R.K., Chang, Y.-Y., Yang, J.-K.: Factors affect on bioremediation of Co(II) and Pb(II) onto Lonicera japonica flowers powder. Desalination Water Treat. 57, 13066–13080 (2016)CrossRefGoogle Scholar
  12. 12.
    Lingamdinne, L.P., Yang, J.-K., Chang, Y.-Y., Koduru, J.R.: Low-cost magnetized Lonicera japonica flower biomass for the sorption removal of heavy metals. Hydrometallurgy 165(Part 1), 81–89 (2016)CrossRefGoogle Scholar
  13. 13.
    Fan, R., Feng, X., Guan, X., Zhang, Q., Luo, Z.: Selective adsorption and recovery of Au(III) from three kinds of acidic systems by persimmon residual based bio-sorbent: a method for gold recycling from e-wastes. Bioresour. Technol. 163, 167–171 (2014)CrossRefGoogle Scholar
  14. 14.
    Ping, Y., Xu, M., Qu, R., Hou, C., Liu, X., Jiang, Z., Qiang, X.: Uptake of gold(III) from waste gold solution onto biomass-based adsorbents organophosphonic acid functionalized spent buckwheat hulls. Bioresour. Technol. 128, 36–43 (2013)CrossRefGoogle Scholar
  15. 15.
    Shan, W., Fang, D., Shuang, Y., Kong, Y., Zhao, Z., Xing, Z., Biswas, B.K., Xiong, Y.: Equilibrium, kinetics, and thermodynamics studies on the recovery of rhenium(VII) and molybdenum(VI) from industrial wastewater by chemically modified waste paper gel. J. Chem. Eng. Data 57, 290–297 (2012)CrossRefGoogle Scholar
  16. 16.
    Prasad, S., Singh, A., Joshi, H.C.: Ethanol as an alternative fuel from agricultural, industrial and urban residues. Resour. Conserv. Recycl. 50, 1–39 (2007)CrossRefGoogle Scholar
  17. 17.
    Chen, S., Yue, Q., Gao, B., Li, Q., Xu, X., Fu, K.: Adsorption of hexavalent chromium from aqueous solution by modified corn stalk: a fixed-bed column study. Bioresour. Technol. 113, 114–120 (2012)CrossRefGoogle Scholar
  18. 18.
    Zheng, L.C., Zhu, C.F., Dang, Z., Zhang, H., Yi, X.Y., Liu, C.Q.: Preparation of cellulose derived from corn stalk and its application for cadmium ion adsorption from aqueous solution. Carbohydr. Polym. 90, 1008–1015 (2012)CrossRefGoogle Scholar
  19. 19.
    Xiong, Y., Wan, L., Xuan, J., Wang, Y.W., Xing, Z.Q., Shan, W.J., Lou, Z.N.: Selective recovery of Ag(I) coordination anion from simulate nickel electrolyte using corn stalk based adsorbent modified by ammonia-thiosemicarbazide. J. Hazard. Mat. 301, 277–285 (2016)CrossRefGoogle Scholar
  20. 20.
    Lou, Z.N., Zhao, Z.Y., Li, Y.X., Shan, W.J., Xiong, Y., Fang, D.W., Yue, S., Zang, S.L.: Contribution of tertiary amino groups to Re(VII) biosorption on modified corn stalk: competitiveness and regularity. Bioresour. Technol. 133, 546–554 (2013)CrossRefGoogle Scholar
  21. 21.
    Wang, F., Zhao, J., Zhou, H., Li, W., Sui, N., Liu, H.: O-carboxymethyl chitosan entrapped by silica: preparation and adsorption behaviour toward neodymium(III) ions. J. Chem. Technol. Biotechnol. 88, 317–325 (2013)CrossRefGoogle Scholar
  22. 22.
    Wang, F., Zhao, J., Wei, X., Huo, F., Li, W., Hu, Q., Liu, H.: Adsorption of rare earths (III) by calcium alginate–poly glutamic acid hybrid gels. J. Chem. Technol. Biotechnol. 89, 969–977 (2014)CrossRefGoogle Scholar
  23. 23.
    Jackson, E.L., Hudson, C.S.: Application of the cleavage type of oxidation by periodic acid to starch and cellulose. J. Am. Chem. Soc. 59, 2049–2050 (1937)CrossRefGoogle Scholar
  24. 24.
    Lucio Anelli, P., Biffi, C., Montanari, F., Quici, S.: Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions. J. Org. Chem. 52, 2559–2562 (1987)CrossRefGoogle Scholar
  25. 25.
    Zheng, L., Dang, Z., Yi, X., Zhang, H.: Equilibrium and kinetic studies of adsorption of Cd(II) from aqueous solution using modified corn stalk. J. Hazard. Mater. 176, 650–656 (2010)CrossRefGoogle Scholar
  26. 26.
    Peppard, D., Mason, G., Lewey, S.: A tetrad effect in the liquid–liquid extraction ordering of lanthanides(III). J. Inorg. Nucl. Chem. 31, 2271–2272 (1969)CrossRefGoogle Scholar
  27. 27.
    Wang, F., Zhao, J., Pan, F., Zhou, H., Yang, X., Li, W., Liu, H.: Adsorption properties toward trivalent rare earths by alginate beads doping with silica. Ind. Eng. Chem. Res. 52, 3453–3461 (2013)CrossRefGoogle Scholar
  28. 28.
    Gładysz-Płaska, A., Majdan, M., Pikus, S.: Adsorption of lanthanides on mordenite from nitrate medium. J. Colloid. Interface Sci. 317, 409–423 (2008)CrossRefGoogle Scholar
  29. 29.
    Langmuir, I.: The constitution and fundamental properties of solids and liquids. Part I. Solids. J. Am. Chem. Soc. 38, 2221–2295 (1916)CrossRefGoogle Scholar
  30. 30.
    Freundlich, H.M.F: Ueber die adsorption in Lesungen. Z. Phys. Chem. 57 A, 385–470 (1906)Google Scholar
  31. 31.
    Temkin, M.J., Pyzhev, V.: Recent modifications to Langmuir isotherms. Acta Physiochim. USSR 12, 217–222 (1940)Google Scholar
  32. 32.
    Guo, J., Cai, J., Su, Q.: Ion imprinted polymer particles of neodymium: synthesis, characterization and selective recognition. J. Rare Earths 27, 22–27 (2009)CrossRefGoogle Scholar
  33. 33.
    Zhang, L., Wu, D., Zhu, B., Yang, Y., Wang, L.: Adsorption and selective separation of neodymium with magnetic alginate microcapsules containing the extractant 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester. J. Chem. Eng. Data 56, 2280–2289 (2011)CrossRefGoogle Scholar
  34. 34.
    Park, H.-J., Tavlarides, L.L.: Adsorption of neodymium(III) from aqueous solutions using a phosphorus functionalized adsorbent. Ind. Eng. Chem. Res. 49, 12567–12575 (2010)CrossRefGoogle Scholar
  35. 35.
    Wang, F., Zhao, J., Li, W., Zhou, H., Yang, X., Sui, N., Liu, H.: Preparation of several alginate matrix gel beads and their adsorption properties towards rare earths (III). Waste Biomass Valor. 4, 665–674 (2013)CrossRefGoogle Scholar
  36. 36.
    Xiong, C.H., Chen, X.Y., Yao, C.P.: Enhanced adsorption behavior of Nd(III) onto D113-III resin from aqueous solution. J. Rare Earths 29, 979–985 (2011)CrossRefGoogle Scholar
  37. 37.
    Lagergren, S.: Zur Theorie Der Sogenannten adsorption Gelöster Stoffe. K. Sven. Vetenskapsakad. Handl. 24, 1–39 (1898)Google Scholar
  38. 38.
    Ho, Y.S.: Adsorption of heavy metals from waste streams by peat. University of Birmingham (1995)Google Scholar
  39. 39.
    Weber, W.J., Morris, J.C.: Kinetics of adsorption on carbon from solution. J. Sanitary Eng. Div. Am. Soc. Civ. Eng. 89, 31–60 (1963)Google Scholar
  40. 40.
    Jeon, C., Nah, I.W., Hwang, K.Y.: Adsorption of heavy metals using magnetically modified alginic acid. Hydrometallurgy 86, 140–146 (2007)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2017

Authors and Affiliations

  • Fuchun Wang
    • 1
  • Junmei Zhao
    • 2
  • Huizhou Liu
    • 2
  • Yuan Luo
    • 1
  • Wankun Wang
    • 1
    Email author
  1. 1.Key Laboratory of Light Metal Materials Processing Technology of Guizhou Provinces, School of Materials and Metallurgical EngineeringGuizhou Institute of TechnologyGuiyangChina
  2. 2.Key Laboratory of Green Process and Engineering, Institute of Process EngineeringChinese Academy of SciencesBeijingChina

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